Water-soluble fiber-reactive disazo dyes, method for producing the same and the use thereof

ABSTRACT

The invention relates to dyes of general formula (1), in which R1 1 , R 2 , M, Z, v and x are defined as cited in claim 1, to the production of the same and to the use of said dyes for colouring or printing material containing hydroxy and/or carbonamide groups, preferably fibrous material

RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. 371)of PCT/EP03/06027 filed Jun. 10, 2003 which claims benefit to Germanapplication Ser. No. 102 25 859.7 filed Jun. 11,2002.

This invention relates to the field of fiber-reactive copper complexdisazo dyes.

Copper complexes of fiber-reactive disazo compounds containing one ormore fiber-reactive groups are known for example from DE-B-1 544 541,DE-B-1 644 155, EP 668 328, DE 32 02 120, EP 085 378, EP 040 806, EP 085378, EP 203 505, DE 3941620, DE 4039866, EP 281898, EP 395951. However,they have certain application defects, for example an excessivedependence of the color yield on varying parameters in the dyeingprocess, or an inadequate or unlevel color build-up on cotton, goodcolor build-up resulting from the ability of a dye to provide a strongerdyeing when used in a higher dye concentration in the dyebath. Moreover,these dyes exhibit unsatisfactory fixation yields, i.e., the portion ofdye permanently fixed to the material to be dyed is too low, especiallyat low temperatures, and also unsatisfactory wash- and lightfastnesses.

However, it is important, for ecological and economic reasons, toprovide dyes having particularly high fixation yields in order that theportion of unfixed dye in the dyehouse effluent may be minimized.Moreover, dyes should always provide uniformly strong dyeings, ideallyregardless of changing dyeing parameters, for example the dyeingtemperature in the dyeing process. Furthermore, washfastnessrequirements are more stringent these days.

The present invention now provides dyes of the general formula (1) whichsurprisingly afford distinctly superior washfastnesses andlightfastnesses coupled with very good build-up. Moreover, these dyeshave higher fixation yields and a distinctly lower parameter dependencein dyeing. They are therefore also more compatible with other dyes whichfix at distinctly lower temperatures.

The invention accordingly provides dyes of the general formula (1):

where

-   -   M is hydrogen, alkali, ammonium or the equivalent of an alkaline        earth metal ion,    -   v is 0 or 1 and    -   Z is —CH═CH₂ or —CH₂CH₂Z¹,        -   where    -   Z¹ is hydroxyl or an alkali-detachable group, and    -   R¹ is hydrogen or C₁–C₄-alkyl;    -   R² is a moiety of the general formulae (2), (3), (4) or (5)

where

-   -   T¹ is hydrogen, methyl, fluorine or chlorine,    -   T² is hydrogen, fluorine or chlorine with the proviso that T²        and T¹ are not both hydrogen;    -   T³ is hydrogen, fluorine or chlorine;    -   A is C₁ to C₄-alkyl which may be substituted by up to two        substituents selected from the group consisting of chloro,        bromo, hydroxyl and carboxyl, C₂ to C₄ alkenyl which may be        substituted by up to two substituents from the group consisting        of chloro, bromo and hydroxyl, or phenyl,    -   L is phenylene or naphthalene, which may be substituted by up to        two substituents selected from the group consisting of chloro,        bromo, hydroxyl, C₁ to C₄-alkyl especially methyl, ethyl, sulfo        and cyano, or else a C₂ to C₆ alkylene;    -   Z is —CH═CH₂, —CH₂CH₂Z¹,        -   where        -   Z¹ is hydroxyl or an alkali-detachable group.

(C₁–C₄)-Alkyl groups A and R¹ can be straight-chain or branched and isin particular selected from the group consisting of methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl.Preference is given to methyl and ethyl. Substituted C₁ to C₄ alkylgroups A are in particular carboxyethyl, carboxypropyl, 1,2-dibromoethylor chloromethyl. Substituted alkyl radicals A are preferably2-bromoethenyl or 2-chloroethenyl.

Examples of preferred R² radicals of the general formula (2) are:2,4-difluoropyrimidin-6-yl, 4,6-difluoropyrimidin-2-yl,5-chloro-2,4-difluoropyrimidin-6-yl,5-chloro-4,6-difluoropyrimidin-2-yl, 4,5-difluoropyrimidin-6-yl,5-chloro-4-fluoropyrimidin-6-yl, 2,4,5-trichloropyrimidin-6-yl,4,5-dichloropyrimidin-6-yl, 2,4-dichloropyrimidin-6-yl,4-fluoropyrimidin-6-yl, 4-chloropyrimidin-6-yl. Particular preference isgiven to R² being 2,4-difluoropyrimidin-6-yl or5-chloro-2,4-difluoropyrimidin-6-yl.

An example of a preferred R² radical of the general formula (3) is2,3-dichloroquinoxaline-6-carbonyl.

Examples of preferred R² radicals of the general formula (4) are acetyl,n-propionyl and n-butyryl; particular preference is given to R² beingacetyl.

Examples of preferred R² radicals of the general formula (5) are3-chloroethylsulfonylbenzoyl and 2-chloroethylsulfonylpropionyl.

In the foregoing general formulae and also in the subsequent generalformulae, the individual symbols, whether they bear identical ordifferent designations within any one general formula, can have meaningsunder their definition which are mutually identical or different.

The dyes of the general formula (1) can possess different fiber-reactivegroups —SO₂Z within the meaning of Z. Examples of alkali-eliminablesubstituents Z¹ in the β-position of the ethyl group of Y or Y′ arehalogen atoms, such as chlorine and bromine, ester groups of organiccarboxylic and sulfonic acids, such as alkylcarboxylic acids, optionallysubstituted benzenecarboxylic acids and optionally substitutedbenzenesulfonic acids, such as the groups alkanoyloxy of 2 to 5 carbonatoms, of which in particular acetyloxy, benzoyloxy, sulfobenzoyloxy,phenylsulfonyloxy and tolylsulfonyloxy, further acidic ester groups ofinorganic acids, as of phosphoric acid, sulfuric acid and thiosulfuricacid (phosphato, sulfato and thiosulfato groups), similarly dialkylaminogroups having alkyl groups of 1 to 4 carbon atoms each, such asdimethylamino and diethylamino.

More particularly, the fiber-reactive groups —SO₂Z can be firstvinylsulfonyl groups and secondly groups —CH₂CH₂Z¹, preferablyβ-thiosulfatoethyl and especially β-sulfatoethylsulfonyl groups.

The groups sulfo, carboxyl, include not only their acid form but alsotheir salt form. Accordingly, sulfo groups are groups conforming to thegeneral formula —SO₃M, carboxyl groups are groups conforming to thegeneral formula —COOM, in each of which M is as defined above.

Preference among the diazo compounds of the general formula (1) is givento those which conform to the general formula (1a)

where M, R¹ and R² are each as defined above.

The dyes of the general formula (1) according to the invention arepreparable for example by diazotization of a substituted aromatic amineof the general formula (6)

and coupling onto a substituted aminonaphthol of the general formula (7)

and subsequent diazotization of the resulting aminomonoazo dye of thegeneral formula (8)

and coupling at a pH of 6 to 9, where appropriate in the presence of adispersant, onto the terminal coupling component of the general formula(9)

followed by a subsequent coppering reaction with copper sulfatepentahydrate.

Diazotizable amines having complexing radicals of the general formula(6) are for example 3-amino-4-hydroxy-5-sulfophenyl β-sulfatoethylsulfone or 3-amino-4-hydroxy-5-sulfophenyl vinyl sulfone.

Compounds of the general formula (7) are for example2-amino-5-hydroxynaphthalene-7-sulfonic acid,2-amino-8-hydroxynaphthalene-6-sulfonic acid,2-amino-5-hydroxynaphthalene-1,7-disulfonic acid and2-amino-8-hydroxynaphthalene-3,6-disulfonic acid.

Compounds of the general formula (8) and (9) are for example known fromEP 0 085 378, EP 0 084 849 and can be prepared by common methods.

The separation and isolation, from the aqueous synthesis solutions, ofthe compounds of the general formula (1) according to the invention canbe effected according to generally known methods for water-solublecompounds, for example by precipitating from the reaction medium bymeans of an electrolyte, such as sodium chloride or potassium chloridefor example, or by evaporating the reaction solution itself, for exampleby spray drying. In the latter case, it is frequently advisable first toprecipitate any sulfate in the solutions as calcium sulfate and removeit by filtration.

The dyes of the invention can be present as a preparation in solid or inliquid (dissolved) form. In solid form, they generally include theelectrolyte salts customary for water-soluble and especially forfiber-reactive dyes, such as sodium chloride, potassium chloride andsodium sulfate, and may further include the auxiliaries customary incommercial dyes, such as buffer substances capable of setting a pH inaqueous solution between 3 and 7, such as sodium acetate, sodium borate,sodium bicarbonate, sodium dihydrogenphosphate, sodium tricitrate anddisodium hydrogen-phosphate, or small amounts of siccatives; if they arepresent in a liquid, aqueous solution (including the presence ofthickeners of the type customary in print pastes), they may also includesubstances which ensure a long life for these preparations, for examplemold preventatives.

In general, the dyes of the invention are present as dye powderscontaining 10 to 80% by weight, based on the dye powder or thepreparation, of an electrolyte salt which is also referred to as astandardizing agent. These dye powders may additionally include theaforementioned buffer substances in a total amount of up to 10% byweight, based on the dye powder. If the dyes of the invention arepresent in aqueous solution, the total dye content of these aqueoussolutions will be up to about 50% by weight, for example between 5 and50% by weight, and the electrolyte salt content of these aqueoussolutions will preferably be below 10% by weight, based on the aqueoussolution; the aqueous solutions (liquid preparations) may include theaforementioned buffer substances in an amount which is generally up to10% by weight, preferably up to 2% by weight.

The dyes of the invention have useful application properties. They areused for dyeing or printing hydroxyl- and/or carboxamido-containingmaterials, for example in the form of sheetlike structures, such aspaper and leather or of films, for example composed of polyamide, or inbulk, as for example of polyamide and polyurethane, but especially fordyeing or printing these materials in fiber form. Similarly, theas-synthesized solutions of the dyes of the invention, if appropriateafter addition of a buffer substance and if appropriate afterconcentrating or diluting, can be used directly as liquid preparationfor dyeing.

The present invention thus also relates to the use of the dyes of theinvention for dyeing or printing these materials and to processes fordyeing or printing these materials in a conventional manner, by usingdyes of the invention as a colorant. The materials are preferablyemployed in the form of fiber materials, especially in the form oftextile fibers, such as woven fabrics or yarns, as in the form of hanksor wound packages.

Hydroxyl-containing materials are those of natural or synthetic origin,for example cellulose fiber materials or their regenerated products andpolyvinyl alcohols. Cellulose fiber materials are preferably cotton, butalso other vegetable fibers, such as linen, hemp, jute and ramie fibers;regenerated cellulose fibers are for example staple viscose and filamentviscose.

Carboxamido-containing materials are for example synthetic and naturalpolyamides and polyurethanes, especially in the form of fibers, forexample wool and other animal hairs, silk, leather, nylon-6,6, nylon-6,nylon-11 and nylon-4.

The dyes of the invention can be applied to and fixed on the substratesmentioned, especially the fiber materials mentioned, by the applicationtechniques known for water-soluble dyes, especially fiber-reactive dyes.

For instance, on cellulose fibers they produce by the exhaust methodfrom a long liquor using various acid-binding agents and optionallyneutral salts, such as sodium chloride or sodium sulfate, dyeings havingvery good washfastnesses. Application is preferably from an aqueous bathat temperatures between 40 and 105° C., optionally at a temperature ofup to 130° C. under superatmospheric pressure, and optionally in thepresence of customary dyeing auxiliaries. One possible procedure is tointroduce the material into the warm bath and to gradually heat the bathto the desired dyeing temperature and to complete the dyeing process atthat temperature. The neutral salts which accelerate the exhaustion ofthe dyes may also, if desired, only be added to the bath after theactual dyeing temperature has been reached.

The padding process likewise provides excellent color yields and verygood color build-up on cellulose fibers, the dyes being allowed tobecome fixed on the material by batching at room temperature or atelevated temperature, for example at up to 60° C., by steaming or usingdry heat in a conventional manner.

Similarly, the customary printing processes for cellulose fibers, whichcan be carried out either single-phase, for example by printing with aprint paste comprising sodium bicarbonate or some other acid-bindingagent and by subsequent steaming at 100 to 103° C., or two-phase, forexample by printing with a neutral or weakly acidic print color andsubsequent fixation either by passing the printed material through a hotelectrolyte-comprising alkaline bath or by overpadding with an alkalineelectrolyte-comprising padding liquor with subsequent batching of thealkali-overpadded material or subsequent steaming or subsequenttreatment with dry heat, produce strong prints with well-definedcontours and a clear white ground. The appearance of the prints is notgreatly affected by variations in the fixing conditions.

When fixing by means of dry heat in accordance with the customarythermofix processes, hot air from 120 to 200° C. is used. In addition tothe customary steam at 101 to 103° C., it is also possible to usesuperheated steam and high-pressure steam at temperatures of up to 160°C.

The acid-binding agents which effect the fixation of the dyes of theinvention on the cellulose fibers include for example water-solublebasic salts of the alkali metals and likewise alkaline earth metals ofinorganic or organic acids or compounds which liberate alkali in theheat. Especially suitable are the alkali metal hydroxides and alkalimetal salts of weak to medium inorganic or organic acids, the preferredalkali metal compounds being the sodium and potassium compounds. Suchacid-binding agents include for example sodium hydroxide, potassiumhydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate,sodium formate, sodium dihydrogenphosphate, disodium hydrogenphosphate,sodium trichloroacetate, waterglass or trisodium phosphate.

The cellulose dyeings obtained following the customary aftertreatment byrinsing to remove unfixed dye portions exhibit very good dye propertiesand provide by the application and fixing methods customary in the artfor fiber-reactive dyes strong dark blue dyeings and prints having verygood fastness properties, especially very good wash-, light-, alkali-,acid-, water-, seawater-, perspiration- and rubfastnesses, on thematerials mentioned in the description, such as cellulose fibermaterials, especially cotton and viscose. The dyeings are furthernotable for their high degree of fixation and good build-up on cellulosematerials. Of particular advantage is the good washfastness of thedyeings, the high fixation value and the low temperature dependencecompared with the prior art.

Furthermore, the dyes of the invention can also be used for thefiber-reactive dyeing of wool. Moreover, wool which has been given anonfelting or low-felting finish (cf. for example H. Rath, Lehrbuch derTextilchemie, Springer-Verlag, 3rd Edition (1972), p. 295–299,especially the finish by the Hercosett process (p. 298); J. Soc. Dyersand Colourists 1972, 93–99, and 1975, 33–44) can be dyed with very goodfastness properties.

The process of dyeing on wool is here carried out in a conventionalmanner from an acidic medium. For instance, acetic acid and/or ammoniumsulfate or acetic acid and ammonium acetate or sodium acetate may beadded to the dyebath to obtain the desired pH. To obtain a dyeing ofacceptable levelness, it is advisable to add a customary leveling agent,for example on the basis of a reaction product of cyanuric chloride with3 times the molar amount of an aminobenzenesulfonic acid and/or of anaminonaphthalenesulfonic acid or on the basis of a reaction product offor example stearylamine with ethylene oxide. For instance, the dyes ofthe invention are preferably subjected to the exhaust process initiallyfrom an acidic dyebath having a pH of about 3.5 to 5.5 under pH controland the pH is then, toward the end of the dyeing time, shifted into theneutral and optionally weakly alkaline range up to a pH of 8.5 to bringabout, especially for very deep dyeings, the full reactive bond betweenthe dyes of the invention and the fiber. At the same time, the dyeportion not reactively bound is removed.

The procedure described herein also applies to the production of dyeingson fiber materials composed of other natural polyamides or of syntheticpolyamides and polyurethanes. In general, the material to be dyed isintroduced into the bath at a temperature of about 40° C., agitatedtherein for some time, the dyebath is then adjusted to the desiredweakly acidic, preferably weakly acetic acid, pH and the actual dyeingis carried out at a temperature between 60 and 98° C. However, thedyeings can also be carried out at the boil or in sealed dyeingapparatus at temperatures of up to 106° C. Since the water solubility ofthe dyes of the invention is very good, they can also be used withadvantage in customary continuous dyeing processes. The dyes of theinvention dye the materials mentioned in deep blue shades.

The examples hereinbelow serve to illustrate the invention. Parts andpercentages are by weight, unless otherwise stated. The compoundsdescribed in the examples in terms of a formula are partly indicated inthe form of free acids; in general these compounds are prepared andisolated in the form of their salts, preferably sodium or potassiumsalts, and used for dyeing in the form of their salts. The startingcompounds mentioned in the following examples, especially tableexamples, can similarly be used in the synthesis in the form of the freeacid or in the form of their salts, preferably alkali metal salts, suchas sodium or potassium salts.

EXAMPLE 1

377 parts of 4-β-sulfatoethylsulfonyl-2-aminophenol-6-sulfonic acid arediazotized with sodium nitrite and coupled at pH 6-7 onto 239 parts of2-amino-5-hydroxynaphthalene-7-sulfonic acid. This monoazo compound

is diazotized and coupled onto 361 parts ofN-acetamino-3,6-disulfo-8-hydroxynaphthalene

The resultant bisazo dye

is subsequently metallized with 245 parts of copper sulfatepentahydrate. The blue dye obtained, which conforms to the formula A

is salted out with sodium chloride, filtered off and dried at 50° C.under reduced pressure. The dye produces strong dark blue dyeings andprints on cotton which have very good fastnesses, among which thelight-, wash-, water- and perspirationfastnesses and also the fastnessto chlorinated water, solvents, crocking and hot pressing may be singledout in particular.

The table examples which follow describe further dyes of the generalformula (1-A) according to the invention. The dyes, when applied by thedyeing methods customary for reactive dyes, provide deep blue dyeingshaving good all-round fastnesses on cotton for example.

(I-A)

Example R² Z 2 —H —CH₂CH₂—OSO₃M 3

″ 4

″ 5

″ 6

″ 7

″ 8

″ 9

—CH₂CH₂—OSO₃M 10

″ 11

″ 12

″ 13

″ 14

″

The process described in example 1 likewise provides the hereinbelowmentioned compounds of the general formula (I-B). When applied by thedyeing methods customary for reactive dyes, they provide yellowish tobrownish red dyeings having good all-round fastnesses on cotton forexample.

(I-B)

Example R² Z 16

—CH═CH₂ 17

—CH₂CH₂—OSO₃H 18

″ 19

—CH₂CH₂—SSO₃H 20

—CH═CH₂

The process described in example 1 likewise provides the hereinbelowmentioned compounds of the general formula (I-C). When applied by thedyeing methods customary for reactive dyes, they provide yellowish tobrownish red dyeings having good all-round fastnesses on cotton forexample.

(I-C)

Example R² Z 21

—CH₂CH₂—OSO₃H 22

″ 23

″ 24

″

1. Dyes of the general formula (1):

where M is hydrogen, alkali, ammonium or the equivalent of an alkalineearth metal ion, v is 0 or 1 and Z is —CH═CH₂ or —CH₂CH₂Z¹, where Z¹ ishydroxyl or an alkali-detachable group, and R¹ is hydrogen orC₁–C₄-alkyl; R² is a moiety of the general formulae (2), (3), (4) or (5)

where T¹ is hydrogen, methyl, fluorine or chlorine, T² is hydrogen,fluorine or chlorine with the proviso that T² and T¹ are not bothhydrogen; T³ is hydrogen, fluorine or chlorine; A is C₁ to C₄-alkylwhich may be substituted by up to two substituents selected from thegroup consisting of chloro, bromo, hydroxyl and carboxyl, C₂ to C₄alkenyl which may be substituted by up to two substituents from thegroup consisting of chloro, bromo and hydroxyl, or phenyl, L isphenylene or naphthalene, which may be substituted by up to twosubstituents selected from the group consisting of chloro, bromo,hydroxyl, C₁ to C₄-alkyl especially methyl, ethyl, sulfo and cyano, orelse is a C₂ to C₆ alkylene; Z is —CH═CH₂, —CH₂CH₂Z¹, Where Z¹ ishydroxyl or an alkali-detachable group.
 2. Dyes as claimed in claim 1wherein R² is a moiety of the general formula (4).
 3. Dyes as claimed inclaim 1 wherein v is
 0. 4. Dyes as claimed in claim 1 wherein the SO₂Zgroup is meta to the azo group.
 5. Dyes as claimed in claim 1, whereinR² is a CH₃CO— radical.
 6. The process for preparing compounds asclaimed in claim 1 by diazotization of a substituted aromatic amine ofthe general formula (6)

and coupling onto the substituted aminonaphthol of the general formula(7)

and subsequent diazotization of the resulting aminomonoazo dye of thegeneral formula (8)

and coupling at a pH of 6 to 9, onto the terminal coupling component ofthe general formula (9)

followed by a subsequent coppering reaction with copper sulfatepentahydrate.
 7. A process for dyeing or printing hydroxyl- and/orcarboxamido-containing material applying one or more dyes as claimed inclaim 1 in dissolved form to the material and fixing the dye or dyes onthe material by means of heat or with the aid of an alkaline agent or bymeans of both heat and with the aid of an alkaline agent.
 8. A dyepreparation comprising a dye as claimed in claim
 1. 9. Dyes as claimedin claim 2, wherein v is
 0. 10. Dyes as claimed in claim 9, wherein theSO₂Z group is meta to the azo group.
 11. Dyes as claimed in claim 10,wherein R² is a CH₃CO— radical.
 12. The process as claimed in claim 7,wherein the material is a fiber material.